Materials Science-Poland, 33(3), 2015, pp.

601-605
http://www.materialsscience.pwr.wroc.pl/
DOI: 10.1515/msp-2015-0091

Structural and optical properties of pure and Ag doped ZnO

thin films obtained by sol gel spin coating technique
S YED M ANSOOR A LI 1∗ , W.A. FAROOQ 1 , M.R. BAIG 1 , M.A. S HAR 2 , M. ATIF 1 ,
S.S. A L G HAMDI 1 , M.S. A L G ARAWI 1 , NAEEM - UR -R EHMAN 3 , M UHAMMAD H AMMAD A ZIZ 4

1 Department of Physics and Astronomy, King Saud University, Riyadh, Saudi Arabia
2 Mechanical Engineering Department, College of Engineering, King Saud University, Riyadh, Saudi Arabia
3 National Centre for Nanotechnology, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering
and Applied Sciences (PIEAS), Islamabad 45650, Pakistan
4 Department of Physics, College of Science, Az Zulfi, Majmaah University, Saudi Arabia

We have investigated the influence of Ag doping on zinc oxide thin films. Pure and Ag doped, preferentially oriented
transparent zinc oxide thin films were prepared by sol gel technique on a glass substrate using diethyl amine as a stabilizer.
The X-ray diffraction analysis revealed that the films with hexagonal wurtzite type structure were polycrystalline in nature with
a preferred grain orientation in the h101i direction. The crystallite sizes decreased from 34 nm to 27 nm after silver doping.
Both photoluminescence and optical transmission measurements showed that the band gap increased after the Ag doping. The
structure and optical characterization studies clearly indicated the incorporation of Ag in ZnO. Hence, the observed increase in
the optical band gap and decrease in crystallite size can be directly attributed to the effect of Ag ion incorporation into the ZnO
lattice.

Keywords: Ag doped ZnO; sol gel; structure properties; optical band gap; defects study
© Wroclaw University of Technology.

1. Introduction O2− and Zn2+ ions, stacked alternately along the

Nanostructure semiconductor materials have a
great importance due to their extraordinary physi-
cochemical properties, which differ from their
bulk counterparts. Zinc oxide (ZnO) is one of
the most attractive materials for developing the
next generation of electronic and optoelectronic
devices [1, 2], such as piezoelectric transducers,
gas sensors, solar cell windows, short wavelength
light emitting diodes, ultraviolet (UV) lasers, pho-
todetectors, etc. [3–8], Zinc oxide (ZnO), a di-
rect wide band gap n-type semiconductor (3.4 eV
at room temperature), has a high exciton bind-
ing energy (60 meV) [1]. It has a stable hexago-
nal wurtzite structure with lattice parameters a =
0.325 nm and c = 0.521 nm, and is composed of
alternating planes with tetrahedrally-coordinated
∗ E-mail: mansoor phys@yahoo.com
c-axis.
ZnO thin films have been prepared by different
deposition techniques, such as pulsed laser depo-
sition [9], r.f. sputtering [10], molecular beam epi-
taxy [11], electron beam evaporation [12], chemi-
cal vapor deposition [13] and spray pyrolysis [14].
In comparison to the other deposition techniques,
the main advantages of sol-gel process are the ex-
cellent compositional control, homogeneous mix-
ing of precursors on a molecular level and low crys-
tallization temperature [15]. Commonly, the sol-
gel technique for the preparation of ZnO thin films
used a solvent of high boiling point, such as ethy-
lene glycol and monoethanolamine. The ZnO films
prepared by using these solvents were highly c-axis
oriented [16–20]. On the other hand, c-axis ori-
ented ZnO thin films were produced even at low
temperature using a solvent of low boiling point,
such as ethanol or isopropanol, and the crystal

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602 S YED M ANSOOR A LI et al.

growth of the thin films was controlled by the tem- substrates are shown in Fig. 1. All the peaks of
perature and heat treatment conditions [17, 18]. the ZnO thin films correspond to the peaks of stan-
Silver is the most interesting among the met- dard ZnO (JCPDS Card No. S6-314). For both the
als because of its remarkable chemical reactivity in samples, (100), (002) and (101) diffraction peaks
solution [21]. Therefore, it is very interesting to un- are observed. In the XRD pattern, the growth of
derstand the role of silver in a transparent conduct- ZnO crystallites along (101) direction shows a pref-
ing oxide ZnO matrix during sol-gel synthesis. In erential c-axis orientation. The doped films have
this paper we report the effect of silver doping on higher and sharper diffraction peaks indicating an
the crystallization behavior, microstructure proper- improvement in intensity with an increase in full
ties and optical properties of ZnO thin films pre- width at half maximum (FWHM) of all the peaks
pared by a sol-gel process. as compared to pure ZnO film. The spectra show
that the film has a polycrystalline structure, which
is typical of a hexagonal wurtzite [19, 20].
2. Experimental
The procedure for preparing pure and Ag-
doped ZnO thin films was as follows. First,
a 0.25 M solution of zinc acetate dehydrate
(Zn(CH3 COO)2 ·2H2 O, Baker, 99.9 %) was dis-
solved in ethanol under magnetic stirring. After
stirring the solution for about 20 min, 10 drops of
diethyl amine was added as a stabilizing agent and
the mixture was further stirred for an hour at 60 °C.
For Ag doping, the silver nitrate (AgNO3 , Aldrich,
99.8 %) was chosen as a doping source. The films
were deposited on a clean glass substrate by spin-
coating method. The spin coating speed and the de-
position time were 3000 rpm and 1 min, respec-
tively. After the spin coating process, the samples Fig. 1. XRD pattern of pure and Ag doped ZnO thin
were dried at 100 °C for 5 min to evaporate the films on glass substrate.
solvent and organic residuals. The process of spin
coating and subsequent pre-heating treatment was In order to obtain detailed information about the
repeated 10 times to obtain a desired thickness. At structure, the crystallite size D along the c-axis was
last, all the samples were annealed at 300 °C for an calculated according to the Scherrer equation [22]:
hour in air.
Crystallinity of the nanostructures was ana- 0.9λ
D= (1)
lyzed with a Bruker diffractometer (XRD) using β cos θ
the CuKα radiation (λ = 1.5406 Å). Optical trans- where D is the crystallite size, λ is the X-ray wave-
mission and reflectance of the thin films were length (λ = 1.5406 Å), β is the full width at half-
studied with a JASCO (V-670) spectrophotome- maximum (FWHM), and θ is the Bragg angle of
ter. The photoluminescence was recorded at room (002) peak. The dislocation density (δ), defined as
temperature. the length of dislocation lines per unit volume, is
estimated using the equation [23]:
3. Results and discussions δ= 1
D2
(2)
The XRD patterns of pure and Ag doped ZnO The lattice constants for the hexagonal structure of
thin film fabricated by sol-gel method on glass pure and doped thin films on glass substrates were

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 Structural and optical properties of pure and Ag doped ZnO thin films. . . 603

determined from the following relations [24]:

4 h2 + hk + k2
 
1 1
= + 2 (3)
d2 3 a2 c
where a, c are the lattice constants and h, k, l are the
Miller indices of the planes, and d is the interplanar
spacing. The Zn–O bond length L is calculated by
the following equation [25]:
s 2
a2

1
L= + − u c2 (4)
3 2

where u parameter in the wurtzite structure is given

by: Fig. 2. Optical transmission spectra of pure and Ag
doped ZnO thin films.
a2
u = 2 + 0.25 (5)
2c
and the absorption edge for a direct band transition
Due to the lattice mismatch between ZnO film and is given by [27]:
glass substrate, some stress can be produced during
the deposition of ZnO thin films. Hence, the strain (αhν)2 = C(hν − Eg) (7)
also significantly changes the structure and prop-
erties of ZnO films to some extent. For ZnO films where C is a constant for a direct transition, h is
with wurtzite structure, the strain can be obtained Planck’s constant, and ν is the frequency of the in-
by the following formula [26]: cident photon. Fig. 3 shows the graph of (αhν)2
c − co vs. photon energy hν (Tauc’s plot) for pure and Ag
ε= × 100% (6) doped ZnO thin films used for calculation of band
co
gap. The linear part of (αhν)2 versus hv at higher
where ε is the mean strain in ZnO thin films, c is photon energies indicates that the pure and doped
the lattice constant of ZnO thin film, and co is the ZnO thin films have direct band transition. The lin-
lattice constant of bulk (standard co = 5. 215 Å). ear portion of the curve, when extrapolated to zero,
The results calculated from the above equations are gives the optical band gap value.
tabulated in Table 1.
The optical transmission spectra of pure and Ag
doped ZnO thin films are shown in Fig. 2. The opti-
cal transmission of pure ZnO is about 87 % in visi-
ble region and after doping it is increased to 89 %.
A weak fluctuation in the spectra is due to inter-
ference phenomena in the thin film. As shown in
Fig. 2, the UV band edge is blue shifted with dop-
ing of Ag, indicating the broadening of the optical
band gap.
For calculation of optical band gap energy (Eg)
of the thin films, first we have assumed the absorp-
tion coefficient α = (1/d)ln(1/T), where T is the
transmittance and d is the film thickness. Hexag-
onal wurtzite structure ZnO has a direct band gap, Fig. 3. Tauc’s plot for calculation of band gap.

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604 S YED M ANSOOR A LI et al.

From the results of Fig. 3, it can be seen that

the energy band gap of the pure and doped ZnO
thin films increased with the Ag doping. This in-
creasing in the energy band gap is known as the
Moss-Burstein shift [28]. Because of this, at high
doping level in zinc oxide films, the donor electrons
occupy the states at the lower edge of conduction
band. Therefore, the optical band gap of Ag doped
zinc oxide is greater than that of pure zinc oxide
films.
The refractive index (n) is an important factor
to fabricate the devices with good optical prop-
erties because the dispersion energy is dependent
on to the optical transition and optical conductiv- Fig. 4. Reflectance spectra of pure and Ag doped ZnO
ity [29]. The value of refractive index for pure and thin films.
Ag doped ZnO thin films were calculated by the
equation 8 [30]:
s √
1+ R
n= √ (8)
1− R
where n is the refractive index and R is the re-
flectance. The measured reflectances for pure and
Ag doped ZnO thin films are shown in Fig. 4. The
inset of Fig. 4 shows the variation of refractive in-
dex with the wavelength for pure and Ag doped
ZnO thin films. It is observed that the refractive in-
dex n for both the films shows similar trend, sharply
decreasing in the wavelength of 320 to 370 and
then, after a sharp increase in the range of 370 to
450 nm, the curve increases slowly with further in- Fig. 5. Photoluminescence spectra of pure and Ag
crease of the wave length. It is also observed that doped ZnO thin films.
the interference peak is shifted toward the longer
wavelength as the Ag concentration increases.
4. Conclusions
The room temperature photoluminescence (PL)
spectra of pure and Ag doped ZnO thin films emis- Pure and Ag doped ZnO thin films were suc-
sion spectra are shown in Fig. 5. There is one dom- cessfully prepared on glass substrates by sol-gel
inant band gap peak in the spectrum of pure ZnO spin coating technique. The effects of Ag doping
at 411 nm. However, in the Ag doped ZnO thin on the structural and optical properties of ZnO thin
film this peak is shifted to 408 nm, which con- films were investigated. Pure and Ag doped de-
firms the increasing of band gap. It is also observed posited films are polycrystalline in nature and the
that two small peaks at 436 and 467 nm in pure crystallite size decreased with Ag doping. It was
ZnO disappear in ZnO doped with Ag, where a new found that optical transmission and refractive index
broad peak at 385 nm has developed. These peaks of Ag doped ZnO were higher than those of pure
in pure and Ag doped ZnO films might be attributed ZnO in the visible wavelength region. It was also
to intrinsic defects, such as oxygen and zinc observed that two small peaks at 436 and 467 nm
interstitials [30]. in pure ZnO disappeared after Ag doping and a

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 Structural and optical properties of pure and Ag doped ZnO thin films. . . 605

Table 1. Structural and optical parameters of pure and Ag doped ZnO thin films.

Crystallite Lattice constant (Å) Dislocation Bond length Strain Band gap Max. Refractive
Sample 14 2
size D (Å) a c δ × 10 (lines/m ) L (Å) ε (%) (eV) transmission (%) index n
ZnO 345 3.256 5.221 8.40 1.948 0.1150 3.217 88 1.40
Ag doped ZnO 280 3.259 5.228 12.75 1.951 0.2492 3.245 90 1.46

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